Synthesis and Properties of Gemini-type Cationic Surfactants Containing Carbonate Linkages in the Linker Moiety Directed Toward Green and Sustainable Chemistry

Gemini-type cationic surfactants containing carbonate linkages as biodegradable and chemically recyclable segments, consisting of two long-chain alkyl groups, two quaternary ammonium groups and a linker moiety, were designed and synthesized as novel green and sustainable cationics with improved physicochemical and biological activities. The gemini-type cationics containing a carbonate linkage showed lower critical micelle concentration values compared to the corresponding single-type cationics. Also, the gemini-type cationics containing a carbonate linkage in the linker moiety showed strong antimicrobial activities. The biodegradability of the gemini-type cationics was significantly improved when a carbonate linkage was introduced into the linker moiety. The maximum biochemical oxygen demand-biodegradability of the gemini-type cationics containing a carbonate linkage in the linker moiety exceeded 70% after a 28-day incubation. Furthermore, the gemini-type cationics containing both a carbonate linkage and an n-dodecyl group showed a chemical recyclability using a lipase (E.C. 3.1.1.3).

Comparison of activities in selective catalytic reduction of NOx by C3H8 over Co/MFI, Fe/MFI, and H/MFI zeolite catalysts

The Co/MFI(SiO₂/Al₂O₃ = 30) were prepared by a precipitation method with NaOCl in alkali solutions exhibited high activities to N₂ at 250 °C for the selective catalytic reduction (SCR) of NO_x. These catalysts showed two UV–vis bands at 700 and 400 nm, indicating the presence of octahedral Co(III) as well as tetrahedral Co(II). The high SCR activity over such Co(III, II)/MFI(30) seems to come from Co(III)---O moieties. The Co(II)MFI(30) catalysts prepared from Co(II)Cl₂ exhibited low SCR activities due to the presence of tetrahedral Co(II) ions in MFI. Less CO formation occurred over Co/MFI catalysts. The Fe/MFI(30) catalyst exhibited high activity due to the presence of some Fe---O species in MFI but more amount of CO were produced during SCR. H/MFI(30) catalyst exhibited a good SCR activity. However, more amount of carbonaceous deposits were produced on it. The correlation between acid concentration and SCR activity was discussed over H/MFIs.     

Kinetic Study of the Prooxidant Effect of α-Tocopherol. Hydrogen Abstraction from Lipids by α-Tocopheroxyl Radical

A kinetic study of the prooxidant effect of α-tocopherol was performed. The rates of allylic hydrogen abstraction from various unsaturated fatty acid esters (ethyl stearate 1, ethyl oleate 2, ethyl linoleate 3, ethyl linolenate 4, and ethyl arachidonate 5) by α-tocopheroxyl radical in toluene were determined, using a double-mixing stopped-flow spectrophotometer. The second-order rate constants (k _p) obtained are <1 × 10⁻² M⁻¹ s⁻¹ for 1, 1.90 × 10⁻² M⁻¹ s⁻¹ for 2, 8.33 × 10⁻² M⁻¹ s⁻¹ for 3, 1.92 × 10⁻¹ M⁻¹ s⁻¹ for 4, and 2.43 × 10⁻¹ M⁻¹ s⁻¹ for 5 at 25.0 °C. Fatty acid esters 3, 4, and 5 contain two, four, and six –CH₂– hydrogen atoms activated by two π-electron systems (–C=C–CH₂–C=C–). On the other hand, fatty acid ester 2 has four –CH₂– hydrogen atoms activated by a single π-electron system (–CH₂–C=C–CH₂–). Thus, the rate constants, k _abstr/H, given on an available hydrogen basis are k _p/4 = 4.75 × 10⁻³ M⁻¹ s⁻¹ for 2, k _p/2 = 4.16 × 10⁻² M⁻¹ s⁻¹ for 3, k _p/4 = 4.79 × 10⁻² M⁻¹ s⁻¹ for 4, and k _p/6 = 4.05 × 10⁻² M⁻¹ s⁻¹ for 5. The k _abstr/H values obtained for 3, 4, and 5 are similar to each other, and are by about one order of magnitude higher than that for 2. From these results, it is suggested that the prooxidant effect of α-tocopherol in edible oils, fats, and low-density lipoproteins may be induced by the above hydrogen abstraction reaction.     

Origin of the Red Color of Satsuma Copper-Ruby Glass as Determined by EXAFS and Optical Absorption Spectroscopy

The origin of the ruby color of Satsuma glass, a famous copper-ruby glass produced in Japan in the mid-19th century, has been examined by electron microprobe analysis (EPMA), X-ray absorption fine structure (XAFS), and optical absorption spectroscopy analyses. Cu K XAFS analysis reveals that the major component of copper in the ruby glass consists of Cu(I) ions in the glass structure. This species is distinct from Cu₂O (cuprite), which we conclude is not responsible for the ruby color. Optical absorption spectra measured at 300 and 77 K clearly distinguishes the absorptions due to the colloidal particles of metallic copper and Cu₂O. It is concluded that the trace amount of copper in the ruby glass, which is below the detection limit of the EPMA and XAFS techniques, exists as metallic copper particles of nanometer size and is responsible for the ruby-red appearance of the Satsuma glass.     

Adaptive interpolation scheme for NURBS curves with the integration of machining dynamics

This paper develops a comprehensive interpolation scheme for non-uniform rational B-spline (NURBS) curves, which does not only simultaneously meet the requirements of both constant feedrate and chord accuracy, but also real-time integrates machining dynamics in the interpolation stage. Although the existing work in this regard has realized the importance to simultaneously consider chord error and machining dynamics, none has really incorporated these in one complete interpolation scheme. In this paper, machining dynamics is considered for three aspects: sharp corners or feedrate sensitive corners on the curves, components with high frequencies or frequencies matching machine natural ones and high jerks. A look-ahead module was developed for detecting and adaptively adjusting the feedrate at the sharp corners. By Fast Fourier Transform (FFT) analysis with a moving window in the interpolation stage identified were some special frequency components such as those containing high frequencies or with frequencies matching machine natural ones. Then, the notch filtering or time spacing method was used to eliminate these components. To more completely reduce feedrate and acceleration fluctuations, the jerk-limited algorithm was also developed. Finally, the interpolated feedrate was further smoothened with B-spline fitting method and the NURBS curves were re-interpolated with the smoothened feedrate. During the interpolation, the chord error was repeatedly checked and confined in the prescribed tolerance. Two NURBS curves were used as examples to test the feasibility of the developed interpolation scheme.     

Mechanochemically synthesized ZIF-8 nanoparticles blended into 6FDA-TrMPD membranes for C3H6/C3H8 separation

The mixed matrix membranes (MMMs) consisting zeolitic-imidazolate framework-8 (ZIF-8) nanoparticles in a polymer have been of considerable interest in separation applications. The fillers used are mostly synthesized using the solvothermal method. In this study, the ZIF-8 nanoparticles were synthesized using a solvent-less and salt-free mechanochemical method and were added to 6FDA-TrMPD polyimide to prepare MMMs. The single gas permeation of C₃H₆ and C₃H₈ through the MMMs was investigated. The C₃H₆ permeability and C₃H₆/C₃H₈ ideal selectivity of a 20 wt% mechano-synthesized ZIF-8/6FDA-TrMPD MMM were 70% and 32% higher than those of the neat polymer membrane at 0.1 MPa and 308 K, respectively. The C₃H₆/C₃H₈ separation performance of the mechano-synthesized ZIF-8 MMM was similar to that of the conventional solvothermal-synthesized ZIF-8 MMM. This separation performance was in good agreement with the Maxwell model. Temperature and pressure dependence analyses confirmed that the mechano-synthesized ZIF-8 nanoparticles acted as molecular sieves in the MMMs for the C₃H₆ and C₃H₈ permeation.     

A study on the optimal fabrication method for micro-scale gyroscopes using a hybrid process consisting of electric discharge machining,chemical etching or micro-mechanical milling

For productive manufacturing of an accurate small-scale wine-glass gyroscope, a hybrid fabrication process consisting of either electric discharge machining, chemical etching, or micro-mechanical milling have been proposed. A comparison of silicon cavity fabrication processes has been conducted in terms of productivity, quality and geometrical accuracy, aiming at the use of the cavity as a mold for creating a thin wall diamond hemisphere, which is the main component of a wine-glass gyroscope. The results have shown that the EDM process, combined with chemical etching, can yield the highest productivity but with limited shape accuracy. The use of mechanical micro-milling, while less productive than EDM and etching, produces a superior quality and geometric accuracy.     

Optical properties of alumina ceramics as a substrate of thin film solar cells

For full understanding of the optical properties of alumina ceramics which are used as a substrate of thin film c-Si solar cells, we carried out computer simulations of diffuse reflectance and measurements of angle-resolved reflectance. As the result of the computer simulations, we obtained a theoretical expression for the reflectance properties of alumina ceramics with flat surface. The expression can be applied for the measured reflectance of alumina ceramics with rough surface when an effect of surface condition was taken into account.     

Application of nuclear energy for environmentally friendly hydrogen generation

It is universally admitted that hydrogen is one of the best energy media and its demand will increase greatly in the near future. However, little hydrogen exists naturally, so that how to generate hydrogen without bringing forth much CO₂${}_2$ will be very important research subject. Hydrogen generation from water using nuclear energy is one of the solutions for this problem. Especially, the high temperature gas cooled reactor (HTGR) has a possibility to generate hydrogen economically compared with other types of nuclear reactors. As for long-lived radioactive waste to be generated by nuclear reactors, it is expected to significantly reduce its burden to the human environment by applying transmutation technologies. This report describes the feature of the hydrogen generation with HTGR and the development of the accelerator-driven subcritical system to reduce radioactive waste ongoing at JAEA.